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Montoya entered the Society of Jesus on 1 November 1606. In the same year, he accompanied Father Diego Torres, the first provincial of Paraguay, to this mission.

In co-operation with Fathers Cataldino and Mazeta, he founded the Reductions of Guayra. He also brought a number of tribal groups into the Catholic Church, and is said to have personally baptized 100,000 Indians. As head of the missions he had charge from 1620 of the "Reductions" on the upper and middle course of the Paraná River, on the Uruguay River, and the Tape River, and added thirteen further "reductions" to the twenty six already existing.

When the missions of Guayra were endangered by the incursions of Paulistas from Brazil in search of slaves, Father Mazeta and Montoya resolved to move the Christian Indians, about 15,000 in number, to the reductions in Paraguay, partly by water with the aid of seven hundred rafts and numberless canoes, and partly by land through the forest. The plan was successfully carried out in 1631. "This expedition", says von Ihering, "is one of the most extraordinary undertakings of this kind known in history" [Globus, LX (1891), 179].

In 1637 Montoya (on behalf of the governor, the Bishop of Paraguay, and the heads of the orders) laid a complaint before Philip IV of Spain as to the Portuguese policy of sending kidnapping expeditions into the neighboring regions. He obtained from the king important exemptions, privileges, and measures of protection for the reductions of Paraguay. Soon after his return to America, Montoya died.

"Silex del Divino Amor" (1640 and unedited in Ruiz de Montoya's times). The first edition was made in 1991, by the Pontifical Catholic University of Lima.

Marion Mulhall calls Ruiz de Montoya's grammar and vocabulary "a lasting memorial of his industry and learning". The German linguist Georg von der Gabelentz regarded them as the very best sources for the study of the Guaraní language, while Hervas declares that the clearness and comprehensive grasp of the rules to which Montoya traced back the complicated structure and pronunciation of Guaraní are most extraordinary. All three works were repeatedly republished and revised. In 1876 Julius Platzmann, the German scholar in native American languages, issued at Leipzig an exact reprint of the first Madrid edition of this work "unique among the grammars and dictionaries of the American languages". A Latin version was edited by the German scholar Christoph Seybold at Stuttgart in 1890-91. A collected edition of all Montoya's works was published at Vienna under the supervision of the Vicomte de Porto Seguro in 1876.

Of much importance as one of the oldest authorities for the history of the Reductions of Paraguay is Montoya's work, Conquista espiritual hecha por los religiosos de la C. de J. en las provincias del Paraguay, Paraña, Uruguay y Tape (Madrid, 1639), in quarto; a new edition was issued at Bilbao in 1892. In addition to the works already mentioned Montoya wrote a number of ascetic treatises.